Probing Phase Formation and Structural Transformations in Sodium Extraction and Insertion of NaFe1−yMnyPO4 through First-Principles Calculations

Manganese (Mn) substitution is a widely explored strategy aimed at sustainably enhancing the energy density of iron (Fe)-based electrode materials by taking advantage of the higher redox potential of the former. However, excessive Mn content can lead to detrimental effects, offsetting the expected i...

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Autores: Ismail, Maha, Lakuntza Irigoien, Oier, Carrasco Rodríguez, Javier, Saurel, Damien, Casas Cabanas, Montserrat, Reynaud, Marine, Saracibar Ruiz de Ocenda, Amaia
Formato: artículo
Fecha de publicación:2024
País:España
Recursos:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/74980
Acesso em linha:http://hdl.handle.net/10810/74980
Access Level:acceso abierto
Palavra-chave:positive electrode materials
olivine NaFePO4
ion batteries
rechargeable lithium phosphate
stability
mechanism
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spelling Probing Phase Formation and Structural Transformations in Sodium Extraction and Insertion of NaFe1−yMnyPO4 through First-Principles CalculationsIsmail, MahaLakuntza Irigoien, OierCarrasco Rodríguez, JavierSaurel, DamienCasas Cabanas, MontserratReynaud, MarineSaracibar Ruiz de Ocenda, Amaiapositive electrode materialsolivine NaFePO4ion batteriesrechargeable lithium phosphatestabilitymechanismManganese (Mn) substitution is a widely explored strategy aimed at sustainably enhancing the energy density of iron (Fe)-based electrode materials by taking advantage of the higher redox potential of the former. However, excessive Mn content can lead to detrimental effects, offsetting the expected improvements. In exper- imental studies, triphylite NaFe0.8Mn0.2PO4 has been identified as an optimal composition with enhanced electrochemical performance compared to that of its parent phase NaFePO4. Higher Mn contents result in a loss of capacity and increased voltage hysteresis. In this study, density functional theory (DFT) calculations were employed to investigate the phase stability upon desodiation of Mn-poor and -rich NaxFe1−yMnyPO4 compositions. Our findings reveal distinct stability behaviors in antagonistic systems NaxFe0.75Mn0.25PO4 and NaxFe0.25Mn0.75PO4, where the presence of Na-vacancies and charge orderings appear to influence phase stability. In addition, the number of intermediate phases throughout the desodiation process is identified as a crucial factor in buffering the volume changes. This work sheds light on the superior electrochemical performance of lightly Mn-substituted phases and unveils a key parameter for designing future electrode materials with improved performance.ACS202520252024info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/74980reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoIngléshttps://pubs.acs.org/doi/10.1021/acs.inorgchem.4c03148info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-nd/4.0/© 2024 American Chemical Society. This publication is licensed under CC-BY-NC-ND 4.0 .oai:addi.ehu.eus:10810/749802026-06-18T09:23:17Z
dc.title.none.fl_str_mv Probing Phase Formation and Structural Transformations in Sodium Extraction and Insertion of NaFe1−yMnyPO4 through First-Principles Calculations
title Probing Phase Formation and Structural Transformations in Sodium Extraction and Insertion of NaFe1−yMnyPO4 through First-Principles Calculations
spellingShingle Probing Phase Formation and Structural Transformations in Sodium Extraction and Insertion of NaFe1−yMnyPO4 through First-Principles Calculations
Ismail, Maha
positive electrode materials
olivine NaFePO4
ion batteries
rechargeable lithium phosphate
stability
mechanism
title_short Probing Phase Formation and Structural Transformations in Sodium Extraction and Insertion of NaFe1−yMnyPO4 through First-Principles Calculations
title_full Probing Phase Formation and Structural Transformations in Sodium Extraction and Insertion of NaFe1−yMnyPO4 through First-Principles Calculations
title_fullStr Probing Phase Formation and Structural Transformations in Sodium Extraction and Insertion of NaFe1−yMnyPO4 through First-Principles Calculations
title_full_unstemmed Probing Phase Formation and Structural Transformations in Sodium Extraction and Insertion of NaFe1−yMnyPO4 through First-Principles Calculations
title_sort Probing Phase Formation and Structural Transformations in Sodium Extraction and Insertion of NaFe1−yMnyPO4 through First-Principles Calculations
dc.creator.none.fl_str_mv Ismail, Maha
Lakuntza Irigoien, Oier
Carrasco Rodríguez, Javier
Saurel, Damien
Casas Cabanas, Montserrat
Reynaud, Marine
Saracibar Ruiz de Ocenda, Amaia
author Ismail, Maha
author_facet Ismail, Maha
Lakuntza Irigoien, Oier
Carrasco Rodríguez, Javier
Saurel, Damien
Casas Cabanas, Montserrat
Reynaud, Marine
Saracibar Ruiz de Ocenda, Amaia
author_role author
author2 Lakuntza Irigoien, Oier
Carrasco Rodríguez, Javier
Saurel, Damien
Casas Cabanas, Montserrat
Reynaud, Marine
Saracibar Ruiz de Ocenda, Amaia
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv positive electrode materials
olivine NaFePO4
ion batteries
rechargeable lithium phosphate
stability
mechanism
topic positive electrode materials
olivine NaFePO4
ion batteries
rechargeable lithium phosphate
stability
mechanism
description Manganese (Mn) substitution is a widely explored strategy aimed at sustainably enhancing the energy density of iron (Fe)-based electrode materials by taking advantage of the higher redox potential of the former. However, excessive Mn content can lead to detrimental effects, offsetting the expected improvements. In exper- imental studies, triphylite NaFe0.8Mn0.2PO4 has been identified as an optimal composition with enhanced electrochemical performance compared to that of its parent phase NaFePO4. Higher Mn contents result in a loss of capacity and increased voltage hysteresis. In this study, density functional theory (DFT) calculations were employed to investigate the phase stability upon desodiation of Mn-poor and -rich NaxFe1−yMnyPO4 compositions. Our findings reveal distinct stability behaviors in antagonistic systems NaxFe0.75Mn0.25PO4 and NaxFe0.25Mn0.75PO4, where the presence of Na-vacancies and charge orderings appear to influence phase stability. In addition, the number of intermediate phases throughout the desodiation process is identified as a crucial factor in buffering the volume changes. This work sheds light on the superior electrochemical performance of lightly Mn-substituted phases and unveils a key parameter for designing future electrode materials with improved performance.
publishDate 2024
dc.date.none.fl_str_mv 2024
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/74980
url http://hdl.handle.net/10810/74980
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c03148
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-nd/4.0/
© 2024 American Chemical Society. This publication is licensed under CC-BY-NC-ND 4.0 .
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-nd/4.0/
© 2024 American Chemical Society. This publication is licensed under CC-BY-NC-ND 4.0 .
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv ACS
publisher.none.fl_str_mv ACS
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,812429

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